Polymerization catalysts and processes therefor

ABSTRACT

Novel catalyst systems which comprise diimine nickel complexes comprising additional ligands selected from the group consisting of acetylacetonate, hexaflourylacetylacetonate, halogens and mixtures thereof can be used with methylaluminoxane in slurry polymerization processes to polymerize mono-1-olefins and, optionally one or more higher mono-1-olefin comonomer(s), to produce high molecular weight polymers.

BACKGROUND

[0001] This invention relates to homopolymerization of mono-1-olefinmonomers, such as ethylene and propylene, and copolymerization of amono-1-olefin monomers, such as ethylene and propylene, with at leastone higher alpha-olefin comonomer.

[0002] It is well known that mono-1-olefins, such as ethylene andpropylene, can be polymerized with catalyst systems employing transitionmetals such as titanium, vanadium, chromium, nickel and/or other metals,either unsupported or on a support such as alumina, silica, titania, andother refractory metals. Supported polymerization catalyst systemsfrequently are used with a cocatalyst, such as alkyl boron and/or alkylaluminum compounds. Organometallic catalyst systems, i.e.,Ziegler-Natta-type catalyst systems usually are unsupported andfrequently are used with a cocatalyst, such as methylaluminoxane.

[0003] It is also well-known that, while no polymer production processis easy, slurry, or loop, polymerization processes are relatively muchmore commercially desirable than other polymerization processes.Furthermore, the type of polymerization process used can have an effecton the resultant polymer. For example, higher reactor temperatures canresult in low catalyst activity and productivity, as well as a lowermolecular weight polymer product. Higher reactor pressures also candecrease the amount of desirable branching in the resultant polymer.

[0004] Most polymer products made in slurry processes, especially thosepolymer products made using supported chromium catalyst systems, have abroader molecular weight distribution and, therefore, the polymerproduct is much easier to process into a final product. Polymers made byother processes, such as, for example, higher temperature and/or higherpressure solution processes, can produce polymers having a narrowmolecular weight distribution; these polymers can be much more difficultto process into an article of manufacture.

[0005] Unfortunately, many homogeneous organometallic catalyst systemshave low activity, high consumption of very costly cocatalysts, likemethylaluminoxane (MAO), and can produce low molecular weight polymerswith a narrow molecular weight distribution. Furthermore, even thoughMAO can be necessary to produce a polymer with desired characteristics,an excess of MAO can result in decreased catalyst system activity.Additionally, these types of homogeneous catalyst systems preferably areused only in solution or gas phase polymerization processes.

SUMMARY OF THE INVENTION

[0006] It is an object of this invention to provide novel catalystsystems useful for polymerization.

[0007] It is another object of this invention to provide catalystsystems which are relatively simple to make, have increased activity andincreased productivity.

[0008] It is a further object of this invention to provide catalystsystems which have reduced cocatalyst consumption.

[0009] It is still another object of this invention to provide animproved polymerization process.

[0010] It is yet another object of this invention to providehomopolymers of mono-1-olefins and copolymers of at least two differentmono-1-olefin(s) that can be processed easily, as indicated by increasedbranching and a broad molecular weight distribution.

[0011] It is still another object of this invention to providehomopolymers of mono-1-olefins and copolymers of at least two differentmono-1-olefin(s) that have an increased molecular weight.

[0012] In accordance with this invention heterogeneous catalyst systemscomprising diimine nickel complexes which further comprise additionalligands selected from the group consisting ofα-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof having a formula selected from the group consisting ofNi(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)₂ and Ni(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)Z andmethylaluminoxane are provided. Processes to make these catalyst systemsalso are provided.

[0013] In accordance with another embodiment of this invention, slurrypolymerization processes comprising contacting ethylene, and optionallyone or more higher alpha-olefins, in a reaction zone with heterogeneouscatalyst systems comprising diimine nickel complexes which furthercomprise additional ligands selected from the group consisting ofα-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof in the presence of methylaluminoxane are provided.

[0014] In accordance with this invention heterogeneous catalyst systemsconsisting essentially of diimine nickel complexes which furthercomprise additional ligands selected from the group consisting of(α-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof and methylaluminoxane are provided. Processes to makethese catalyst systems also are provided.

[0015] In accordance with another embodiment of this invention, slurrypolymerization processes consisting essentially of contacting ethylene,and optionally one or more higher alpha-olefins, in a reaction zone withheterogeneous catalyst systems comprising diimine nickel complexes whichfurther comprise additional ligands selected from the group consistingof α-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof in the presence of methylaluminoxane are provided.

[0016] In accordance with yet another embodiment of this invention,compositions comprising homopolymers of ethylene and copolymers ofethylene and one or more higher alpha-olefins which can be characterizedas having high molecular weight, increased branching and a broadmolecular weight distribution, are provided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Catalyst Systems

[0017] Catalyst systems of this invention can be characterized asdiimine nickel complexes comprising additional ligands selected from thegroup consisting of β-diketonates, halogens and mixtures thereof havinga farmula selected from the group consisting ofNi(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)₂ and Ni(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)Z and alsorepresented by general structural formulas as shown below in Compounds Iand II,

[0018] wherein R can be the same or different and is selected from thegroup consisting of branched or linear alkyl or aromatic groups havingfrom about 1 to about 10, preferably from about 1 to about 8, carbonatoms per alkyl group and R can be in any position on the aromatic ring;and

[0019] R′ can be the same or different and is selected from the groupconsisting of hydrogen and linear, branched, cyclic, bridging, aromatic,and/or aliphatic hydrocarbons, having from about 1 to about 70,preferably from about 1 to about 20, carbon atoms per radical group.

[0020] R substituents on the aromatic rings of the diimine nickelcomplex can be the same or different, and are selected from the groupconsisting of branched or linear alkyl (aliphatic) or aromatic groupshaving from about 1 to about 10, preferably from about 1 to about 8,carbon atoms per alkyl group. Although hydrogen can be used, hydrogencan inhibit synthesis of the ligand. R groups having more than about 8carbon atoms per group can result in a catalyst system with loweractivity and/or productivity. While not wishing to be bound by theory,it is believed that larger substituent groups can cause steric hindrancein the catalyst system, thereby which can decrease catalyst systemactivity and/or productivity and/or ease of synthesis of the catalyst.Exemplary alkyl substituents are selected from the group consisting ofmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, benzyl,phenyl groups, and mixtures of two or more thereof. Preferably, the Rsubstituent is an electron-donating species, selected from the groupconsisting of linear or branched aliphatic groups having from about 1 toabout 5 carbon atoms per group. Most preferably, the R groups are boththe same and are selected from the group consisting of methyl andisopropyl, due to commercial availability and ease of synthesis of theligand.

[0021] The R group can be in any position, i.e., from 2 to 6, on thearomatic ring. Preferably, the R group, which can be the same ordifferent, is either in the 2 or 6 position, due to ease of synthesis.Most preferably, for best catalytic activity and productivity, both Rgroups are the same and are in the 2 and 6 positions on the aromaticring.

[0022] R′ substituents can be the same or different and are selectedfrom the group consisting of hydrogen and branched, linear, cyclic,aromatic or aliphatic radicals having from about 1 to about 70 carbonatoms per radical. Further, the R∝ substituents can be linked, orjoined, across the carbon-carbon bridge between the two nitrogen atoms.While not wishing to be bound by theory, it is believed that radicalshaving more than 70 carbon atoms can add to the steric hindrance of thecatalyst systems and hinder catalyst synthesis and/or activity andproductivity. Preferably, the R′ substituent group is selected from thegroup consisting of hydrogen and branched, linear, cyclic, aromatic oraliphatic radicals having from about 1 to about 20 carbon atoms perradical, due to commercial availability and ease of synthesis of theligand. Most preferably, the R′ substituent groups are the same or alink across the carbon-carbon bridge between the nitrogen atoms, and theR′ substituent is selected from the group consisting of hydrogen andbranched, linear, cyclic, aromatic or aliphatic radicals having fromabout 1 to about 12 carbon atoms per radical, for the reasons givenabove. Exemplary R′ substituents include, but are not limited to,hydrogen, methyl, ethyl, propyl, phenyl, taken together acenaphthyl orcyclobutadienyl. Preferably, the R′ substituents are identical and areselected from the group consisting of hydrogen, methyl and acenaphthylfor best resultant catalyst system activity and productivity.

[0023] R″CYCXCYR″ substituents, or ligands, in which R″ can be the sameor different, on the diimine nickel complex can be the same or differentand are selected from the group consisting ofα-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof. The α-deprotonated-β-diketones andα-deprotonated-β-ketoesters can be derived from β-diketone andβ-ketoester ligand precursors. Exemplary ligands precursors include, butare not limited to, compounds selected from the group consisting of2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione,allylacetonacetate, benzoylacetonate, benzoyl-1,1,1-trifluoroacetone,1,1,1-trifluoro-2,4-pentanedione, 1-chloro-1,1-difluoroacetylacetonemethyl-4,4,4-trifluoroacetoacetate,1,1,1-trifluoro-5,5-dimethyl-2,4-pentanedione, ethylα-methyl-4,4,4-trifluoroacetoacetate,4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, and2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione. Preferably,ligand precursors are selected from the group consisting of2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione,1,1,1-trifluoro-2,4-pentanedione, 1-chloro-1,1-difluoroacetylacetone,methyltrifluoroacetoacetate,1,1,1-trifluoro-5,5-dimethyl-2,4-pentanedione, and ethylα-methyl-4,4,4-trifluoroacetoacetate. Most preferably, ligands include,but are not limited to 2,4-pentanedione,1,1,1,5,5,5-hexafluoro-2,4-pentanedione,1,1,1-trifluoro-2,4-pentanedione, 1-chloro-1,1-difluoroacetylacetone,and 1,1,1-trifluoro-5,5-dimethyl-2,4-pentanedione for best catalystsystem activity as well as best polymer product properties.

[0024] The group Z, i.e., halogen, of the diimine nickel complex isselected from the group consisting of fluorine, chlorine, bromine and/oriodine. Preferably, the halogen is selected from the group consisting ofchlorine and/or bromine for high catalyst activity and productivity.Most preferably, the halogen is chlorine for best catalyst systemactivity and productivity.

[0025] The diimine nickel complex catalyst system disclosed in thisapplication can be prepared by any method known in the art. For example,approximate molar equivalents of a diimine ligand and a nickel compoundcan be contacted in the presence of any compound that can dissolve boththe diimine ligand and nickel compound, either partially or completely.The contacting conditions can be any conditions suitable to effect theformation of a diimine nickel complex. Preferably, for best productresults, the diimine ligand/nickel complex mixture is contacted at roomtemperature under a dry atmosphere for any amount of time sufficient toform the diimine nickel complex. Completion of the—formation of thediimine nickel complex can be evidenced by a color change. Generally,contacting times of about 8, and preferably 12 hours are sufficient.Usually, as a result of the preparation procedure, the resultant diiminenickel complex will comprise from about 3 to about 20, preferably fromabout 5 to about 15, weight percent nickel, based on the total mass ofthe diimine nickel complex. The presence of oxygen is not thought to bedetrimental to this aspect of the preparation procedure.

[0026] In general, diimine ligands are contacted with a nickelβ-diketonate or nickel β-diketonate halide to form diimine nickelcomplexes. Typical syntheses of nickel complexes related to thosedescribed in this invention can be found in Dieck, H., Svboda, M., andGreiser, T., Z. Naturforsch B: Anorg. Chem. Organ. Chem., Vol. 36b, pp.823-832 (1981), herein incorporated by reference. Usually for ease ofcatalyst system preparation, the diimine ligand is prepared first. Thecatalyst preparation procedure can vary, depending on the substituentson the diimine ligand. For example, to prepare a specific diimineligand, wherein R′ is hydrogen, a three-component mixture is prepared. Atwo-fold molar excess of aniline, containing the desired R substituents(R_(n)C₆H_(7-n))N, wherein n=1,2), is contacted with a dialdehyde, suchas, for example, glyoxal (CHOCHO), in the presence of a compound capableof being a solvent for both organic and aqueous compounds. Exemplarysolvents for both organic and aqueous compounds include, but are notlimited to, methanol, ethanol and/or tetrahydrofuran (THF). The mixturecan be contacted, preferably refluxed, under any atmosphere to form thedesired ligand. Preferably, the mixture is refluxed for at least 10,preferably 20 minutes, cooled and the desired ligand can be recovered.Generally, after refluxing and cooling, the ligand can be recovered in acrystalline form.

[0027] To prepare another specific diimine ligand wherein the R′ groupis anything other than hydrogen, a similar procedure can be used. Forexample, at least a two-fold molar excess of aniline or a substitutedaniline can be combined with a compound capable of dissolving bothorganic and aqueous compounds and a very minor amount of formic acid.Then, about a one molar equivalent of an alpha-diketone (R′COCOR′) canbe added to the mixture. The mixture can be stirred, under atmosphericconditions of temperature and pressure until the reaction is completeand the desired ligand is formed. Preferably, water is absent from thereaction mixture. Generally, the reaction will be complete in about 18,preferably 24 hours. A crystalline ligand product can be recoveredaccording to any method known in the art.

[0028] The nickel bis(β-diketonate), nickel bis(β-ketoester), nickelβ-diketonate halide and nickel β-ketoester halide can be prepared by anymethod known in the art. Typical syntheses of such nickel complexes canbe found in Bullen, G. J., Mason, R., and Pauling, P., InorganicChemistry, Vol. 4, pp. 456-462 (1965), herein incorporated by reference.Alternatively, and especially in the case of nickel β-diketonate halidesand nickel β-ketoester halides, the salt of the β-diketone orβ-ketoester can be prepared then reacted with the correct quantity ofnickel halide. A mixture of an appropriate Brönsted base, such as butnot limited to sodium or potassium hydride or sodium or potassiummethoxide, is mixed with a solvent capable of dissolving or becomingmiscible with the β-diketone or β-ketoester. Exemplary solvents includetoluene, benzene, methanol, or ethanol. One molar equivalent of theβ-diketone or β-ketoester is added slowly to this mixture. Reaction isknown to occur as evidenced by the evolution of heat and a change in thephysical appearance of the mixture. Once all reactants have contacted,reaction times from 4 to 12 hours are sufficient to ensure completereaction. If the product salt of the β-diketone or β-ketoester is notsoluble in the solvent chosen, the solvent is removed by filtration orvacuum and the salt dissolved in a solvent in which it is soluble.Exemplary solvents include methanol and ethanol. This solution is thenadded to a one half molar equivalent of nickel halide that has beensuspended or dissolved in the same solvent or a solvent with which thefirst solvent is miscible. The preceding reactant ratio results in theformation of the nickel bis(β-diketonate) or nickel bis(β-ketoester). Ifthe nickel β-diketonate halide or nickel β-ketoester halide are desired,the solution is added to one molar equivalent of nickel halide asdescribed. Reaction is known to occur as evidenced by the formation of asoluble green species. Reaction times of 4 to 12 hours are sufficient toensure complete reaction. The byproduct sodium or potassium halide saltis then removed from the reaction product by filtration and/orcentrifugation. The solvent is removed by vacuum to yield the nickelcomplex used in the nickel diimine complex synthesis.

[0029] After formation of a diimine nickel complex, the diimine nickelcomplex can be recovered by any method known in the art, such as, forexample evaporation and/or vacuum filtration of the solvent. Further, ifdesired, the diimine nickel complex can be further purified by washing.One exemplary wash compound can be heptane. The diimine nickel complexcatalyst system can be recovered and used as a solid, heterogeneouscatalyst system.

Reactants, Polymerization and Polymer Products

[0030] Polymers produced according to the process of this invention canbe homopolymers of mono-1-olefins or copolymers of at least twodifferent mono-1-olefins. Exemplary mono-1-olefins useful in thepractice of this invention include, but are not limited tomono-1-olefins having from about 2 to about 10 carbon atoms permolecule. Preferred mono-1-olefins include, but are not limited toethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, 1-nonene and 1-decene.If the reaction product is a copolymer, one mono-1-olefin monomer can bepolymerized with a mono-1-olefin comonomer which is a differentalpha-olefin, usually having from about 3 to about 10, preferably from 3to 8 carbon atoms per molecule. Exemplary comonomers include, but arenot limited to, propylene, 1-butene, butadiene, 1-pentene, 1-hexene,1-octene, 4-methyl-1-pentene, and mixtures thereof. Preferably, if themonomer is ethylene, the comonomer is 1-hexene and/or4-methyl-1-pentene, in order to achieve maximum polymer producttoughness. Preferably, if the monomer is propylene, the comonomer isethylene and/or butadiene in order to achieve maximum polymer producttoughness and clarity.

[0031] If a comonomer is used, the comonomer can be added to thepolymerization reactor, or reaction zone, in an amount within a range ofabout 1 to about 20 weight percent, preferably within 7 to about 18weight percent, based on the weight of the ethylene monomer. Mostpreferably, a comonomer is present in the reaction zone within a rangeof about 10 to about 16 weight percent, in order to produce a polymerhaving the most desired physical properties.

[0032] Polymerization of the monomer and optional comonomer must becarried out under slurry, also known as loop/slurry or particle form,polymerization conditions wherein the temperature is kept below thetemperature at which polymer swells significantly. Slurry polymerizationprocesses are much easier to operate and maintain than otherpolymerization processes; a polymer product produced by a slurry processcan be recovered much more easily. Such polymerization techniques arewell-known in the art and are disclosed, for instance, in Norwood, U.S.Pat. No. 3,248,179, the disclosure of which is hereby incorporated byreference.

[0033] The slurry process generally is carried out in an inert diluent(medium), such as, for example, a paraffin, cycloparaffin, and/oraromatic hydrocarbon. Preferably, the inert diluent is an alkane havingless that about 12 carbon atoms per molecule, for best reactor operationand polymer product. Exemplary diluents include, but are not limited topropane, n-butane, isobutane, n-pentane, 2-methylbutane (isopentane),and mixtures thereof. Isobutane is the most preferred diluent due to lowcost and ease of use.

[0034] The temperature of the polymerization reactor, or reaction zone,when using isobutane as the reactor diluent, according to thisinvention, is critical and must be kept within a range of about 5° toabout 100° C. (41°-212° F.) and preferably within a range of about 10°to about 70° C. (50°-158° F.). Most preferably, the reaction zonetemperature is within a range of 20° to 60° C. (68°-140° F.) for bestcatalyst activity and productivity. Reaction temperatures below about10° C. can be ineffective for polymerization.

[0035] Pressures in the slurry process can vary from about 100 to about1000 psia (0.76-7.6 MPa), preferably from about 200 to about 700 psia.Most preferably, the reaction zone is maintained at a pressure within arange of 300 to 600 psia for best reactor operating parameters and bestresultant polymer product. The catalyst system is kept in suspension andis contacted with the monomer and comonomer(s) at sufficient pressure tomaintain the medium and at least a portion of the monomer andcomonomer(s) in the liquid phase. The medium and temperature are thusselected such that the polymer or copolymer is produced as solidparticles and is recovered in that form. Catalyst system concentrationsin the reactor can be such that the catalyst system content ranges from0.001 to about 1 weight percent based on the weight of the reactorcontents.

[0036] The catalyst system and methylaluminoxane (MAO) can be added tothe reactor in any order to effect polymerization. For example, catalystsystem can be added, then some reactor diluent, such as isobutane,followed by MAO, then more diluent and finally, monomer and optionalcomonomer. However, as stated earlier, this addition order can bevaried, depending on equipment availability and/or desired polymerproduct properties. Preferably, the catalyst system and MAO are notprecontacted prior to addition to the polymerization reactor due to apossible decrease in catalyst activity.

[0037] The amount of catalyst system and MAO added to the reactor canvary. Generally, a molar excess of MAO is present, relative to thediimine nickel complex. Preferably, the aluminum to nickel (A1:Ni) molarratio is less than about 1500:1, more preferably within a range of about50:1 to about 600:1. Most preferably, the molar ratio of aluminum tonickel is within a ratio of 100:1 to 400:1 for best catalyst systemactivity and productivity.

[0038] Two preferred polymerization methods for the slurry process arethose employing a loop reactor of the type disclosed in Norwood andthose utilizing a plurality of stirred reactors either in series,parallel or combinations thereof wherein the reaction conditions can bethe same or different in the different reactors. For instance, in aseries of reactors, a chromium catalyst system which has not beensubjected to the reduction step can be utilized either before or afterthe reactor utilizing the catalyst system of this invention.

[0039] Polymers produced in accordance with this invention generallyhave a relatively narrow heterogeneity index (HI), which is a ratio ofthe weight average molecular weight (M_(w)) and the number averagemolecular weight (M_(n)) (also expressed as M_(w)M_(n)). Polymersproduced in accordance with this invention usually have a HI within arange of about 3 to about 10, preferably within a range of about 3 toabout 6, for best indication of processability.

[0040] Polymers produced in accordance with this invention are veryunique because of a significant amount of short chain branching whichcan be produced even in the absence of a comonomer added to the reactor.This short chain branching is evidence that some sort of comonomers areproduced in-situ in the reactor and are incorporated into the polymerand/or that the catalyst can form short chain branches by rearrangementof the main polymer chain through successive hydride elimination, olefinrotation, and hydride re-addition reactions. This series of steps maynot involve discrete intermediates and may rather be a concerted orcontinuous series of reactions with no distinct intermediates formed.Such rearrangements can be termed “chain walking”. Chain walking can bedescribed by the active metal catalyst, i.e. nickel, “walking” adistance along the polymer backbone during polymerization and hence, theshort chain branch length can be dictated by the rate of ethyleneinsertion relative to the combined rates of hydride elimination, olefinrotation, and hydride re-addition. Usually polymers produced inaccordance with this invention, wherein no comonomer is added to thepolymerization reactor comprise up to about 3000, and generally fromabout 20 to about 3000 short chain branches per 10,000 (or from about 2to about 300 short chain branches per 1000) backbone carbon atoms of thepolymer. Furthermore, the short chain branches produced comprise bothodd and even carbon branches, i.e., branches comprising an odd number ofcarbon atoms per short chain branch, as well as branches comprising aneven number of carbon atoms per short chain branch.

[0041] If desired, optional addition of one or more comonomers can beadded to the polymerization reactor. The affirmatively added comonomerscan further increase the amount of short chain branching in theresultant polymer, or copolymer. Polymers produced with the addition ofa comonomer can have a greater number of short chain branches inaddition to those generated as described above. If a comonomer isaffirmatively added to the polymerization reactor, these polymersusually can comprise up to about 3500, and generally from about 20 toabout 3500, short chain branches per 10,000 backbone carbon atoms ofpolymer.

[0042] A further understanding of the invention and its advantages isprovided by the following examples.

EXAMPLES

[0043] The following Examples illustrate various aspects of theinvention. Data are included for each example about polymerizationconditions, as well as the resultant polymer. All chemical handling,including reactions, preparation and storage, was performed under a dry,inert atmosphere (usually nitrogen). Unless otherwise indicated, benchscale polymerizations were completed in a 2.6 liter autoclave reactor atthe desired temperature using an isobutane (1.2 liter) slurry. Thereactor was heated to 120° C. and purged with nitrogen for about 20minutes. The reactor then was cooled to the desired polymerizationtemperature and pressurized with isobutane to about 400 psig. A knownquantity (mass) of diimine nickel complex catalyst was charged to thereactor against a countercurrent of isobutane and the agitator was setat 490 rpm. If hydrogen was charged to the reactor, hydrogen additionwas followed by isobutane. The desired quantity of methylaluminoxane(MAO) (10 weight % in toluene) was charged directly to the reactor viasyringe. After the full volume of isobutane was added, ethylene wasadded to bring the total reactor pressure to 550 psig. Ethylene was fedon demand and the polymerization reaction terminated when ethylene flowinto the reactor ceased. Run times for each polymerization reaction areprovided in the Tables.

[0044] The abbreviations for the catalyst systems used are as follows:

[0045][(iPr₂Ph)₂DABMe₂]Ni(acac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(acetylacetonate)

[0046][(iPr₂Ph)₂DABMe₂]Ni(hfacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(1,1,1,5,5,5-hexafluoroacetylacetonate)

[0047][(iPr₂Ph)₂DABMe₂]Ni(hfacac)Cl-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) (1,1,1,5,5,5-hexafluoroacetylacetonate)chloride

[0048][(iPr₂Ph)₂DABMe₂]Ni(allOacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminebis(allylacetylacetonato) nickel (II)

[0049][(iPr₂Ph)₂DABMe₂]Ni(Phacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(benzoylacetonate)

[0050][(iPr₂Ph)₂DABMe₂]Ni(PhCF₃acac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(benzoyl-1,1, 1-trifluoroacetonate)

[0051][(iPr₂Ph)₂DABMe₂]Ni(CF₃acac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(1,1,1-trifluoroacetylacetonate)

[0052][(iPr₂Ph)₂DABMe₂]Ni(CClF₂acac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(1-chloro-1,1-difluoroacetylacetonate)

[0053][(iPr₂Ph)₂DABMe₂]Ni(CF₃MeOacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminebis(methyltrifluoroacetoacetonato) nickel(II)

[0054][(iPr₂Ph)₂DABMe₂]Ni(CF₃tBuacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(1,1,1-trifluoro-5,5-dimethylacetylacetonate)

[0055][(iPr₂Ph)₂DABMe₂]Ni(CF₃OEt-α-Meacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminebis(ethyl α-methyl-4,4,4-trifluoroacetoacetato) nickel(II)

[0056][(iPr₂Ph)₂DABMe₂]Ni(CF₃furacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(4,4,4-trifluoro-1-(2-furyl)acetylacetonate)

[0057][(iPr₂Ph)₂DABMe₂]Ni(CF₃CF₂CF₂tBuacac)₂-N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediiminenickel(II) bis(2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate)

[0058][(iPr₂Ph)₂DABAn]Ni(hfacac)₂-N,N′-bis(2,6-diisopropylphenyl)acenaphthylnickel(II) bis(hexafluoroacetylacetonate)

[0059][(Me₂Ph)₂DABH₂]Ni(acac)₂-N,N′-bis(2,6-dimethylphenyl)-2,3-ethylenediiminenickel(II) bis(acetylacetonate)

[0060][(Me₂Ph)₂DABMe₂]Ni(acac)₂-N,N′-bis(2,6-dimethylphenyl)-2,3-butanediiminenickel(II) bis(acetylacetonate).

[0061] In general, catalyst systems used for polymerization in theExamples were prepared as described in this application.

[0062] Mass Catalyst (grams) is the mass of catalyst system charged tothe polymerization reactor for each Run. Polymer density was determinedin grams per cubic centimeter (g/cc) on a compression molded sample,cooled at about 15° C. per hour, and conditioned for about 40 hours atroom temperature in accordance with ASTM D1505 and ASTM D1928, procedureC. High load melt index (HLMI, g/10 mins) was determined in accordancewith ASTM D1238 at 190° C. with a 21,600 gram weight. Melt index (MI,g/10 mins) was determined in accordance with ASTM D1238 at 190° C. witha 2,160 gram weight. Size exclusion chromatography (SEC) analyses wereperformed at 140° C. on a Waters, model 150 GPC with a refractive indexdetector. A solution concentration of 0.17 to 0.65 weight percent in1,2,4-trichlorobenzene was found to give reasonable elution times.Reported weight average molecular weight (Mw) and number averagemolecular weight (M_(n)) values (results) need to be multiplied by afactor of 1000 for the actual value. Reported Al:Ni ratio values areexpressed as molar ratio values. Values that were not determined arerepresented as “ND” in the Tables.

Example 1

[0063] This example shows that high catalyst system productivity can beachieved by substituting one or both of the halide ligands of a diiminenickel dihalide complex with a β-diketonate or β-ketoester ligand.

[0064] Polymerizations in the following Runs were carried out asdescribed above, with a reactor pressure of 550 psig ethylene inisobutane slurry at 40° C. MAO was added in a 10% wt/wt solution intoluene. Polymerization results are listed below in Table 1. TABLE 1 RunMass Run Time Productivity Density # Catalyst cat. (g) (mins.) (g PE/gNi) MI HLMI (g/cc) Al:Ni 101 [(iPr₂Ph₂)DABMe₂]NiBr₂ 0.0218 13  490 ND NDND 240 102 [(iPr₂Ph₂)DABMe₂]Ni(CF₃CF₂CF₂tBuacac)₂ 0.0583  4  7310 0 00.9196 150 103 [(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0200  9 11400 0 0 0.9099 230 104[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0050  4 12000 ND ND ND 1200  105[(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0230 30 13400 0 0 0.9081 200 106[(iPr₂Ph₂)DABMe₂]Ni(CF₃OEt-α-Meacac)₂ 0.0163 21 13900 0 0 0.9074 450 107[(iPr₂Ph₂)DABMe₂]Ni(Phacac)₂ 0.0109 18 17100 ND ND 0.9212 610 108[(iPr₂Ph₂)DABMe₂]Ni(allOacac)₂ 0.0209 27 21300 0 0 0.9157 300 109[(iPr₂Ph₂)DABMe₂]Ni(CF₃acac)₂ 0.0020  8 29500 0 0 ND 3300  110[(iPr₂Ph₂)DABMe₂]Ni(CF₃furacac)₂ 0.0121 17 30700 0 0 0.8961 610 111[(iPr₂Ph₂)DABMe₂]Ni(PhCF₃acac)₂ 0.0165 41 33700 0 0 0.9137 460 112[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0111  3 35000 0 0 0.8819 670 113[(iPr₂Ph₂)DABMe₂]Ni(CClF₂acac)₂ 0.0118 10 96200 0 0 0.8857 580 114[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0195 15 108000  0 0 0.8926 ND 115[(iPr₂Ph₂)DABMe₂]Ni(tBuCF₃acac)₂ 0.0114 17 139000  ND ND 0.8918 640 116[(iPr₂Ph₂)DABMe₂]Ni(CF₃acac)₂ 0.0041 60 157000  0 0 0.8955 1600  117[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0092 18 174000  0 0 0.8888 810 118[(iPr₂Ph₂)DABMe₂]Ni(hfacac)Cl 0.0062 27 198000  0 0 0.8871 1000  119[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0052 31 293000  0 0 0.9100 860 120[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0100 31 327000  0 0 0.9087 750 121[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0025 14 378000  0 0 0.9017 600 122[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0040 35 493000  0 0 0.9111 750 123[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0052 31 621000  0 0  0.88531 14001 

[0065] The data in Table 1 show that diimine nickel(II) catalyst systemscontaining β-diketonate or β-ketoester ligands can effectivelypolymerize ethylene with higher productivity than catalysts containingexclusively diimine and halide ligands (see Runs 101, 103 and 105). Thedata also show that the addition of a single β-diketonate ligand affordsmuch higher productivity. Also note that reactor temperatures are withincommercially acceptable ranges, i.e., between 40 and 80° C.

Example 2

[0066] This example shows that process conditions can be changed withoutlosing the high productivity attained by one, or both of the halideligands of a diimine nickel dihalide complex with a β-diketonate orβ-ketoester ligand. Again, all of the following polymerizations werecarried out as described above, with a reactor pressure of 550 psigethylene in isobutane slurry. MAO was added in a 10% wt/wt solution intoluene. Process conditions were varied by changing the polymerizationtemperature and, as a result, the quantity of dissolved ethylene in thereaction medium. The structure of the diimine ligand was also varied.Polymerization catalyst systems and results are listed below attemperatures of 27, 60, and 80° C. in Tables 2, 3, and 4, respectively.TABLE 2 (all Runs were at 27° C.) Run Run Mass Time Productivity Density# Catalyst cat. (g) (mins.) (g PE/g Ni) MI HLMI (g/cc) Al:N Mn Mw HI 201[(iPr₂Ph₂)DABMe₂]NiBr₂ 0.0340 15  940 ND ND 0.9450 160 ND ND ND 202[(iPr₂Ph₂)DABAn]NiBr₂ 0.0303 25  1210 ND ND 0.9564 200 ND ND ND 203[(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0231 24  1580 ND ND ND 200 ND ND ND 204[(Me₂Ph₂)DABMe₂]NiBr₂ 0.0301 17  2020 0 0.05 0.9496 140 239  531 2.22205 [(Me₂Ph₂)DABH₂]NiBr₂ 0.0294 24  2510 1.4 84 0.9749 140  20  74 3.64206 [(iPr₂Ph₂)DABAn₂]NiCl₂ 0.0343 31  4080 0 0 0.9421 160 399 1059 2.65207 [(Me₂Ph₂)DABH₂]NiCl₂ 0.0233 31  4950 0.46 38 0.9691 140 ND ND ND 208[(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0176 41 26900 0 0 0.9175 260 ND ND ND 209[(Me₂Ph₂)DABMe₂]NiCl₂ 0.0413 60 27900 0 0.07 0.9457  87  95  373 3.92210 [(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0362 30 29000 0 0.45 0.9305 120 ND ND ND211 [(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0021  9 42300 0 0.07 0.9383 420 ND ND ND212 [(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0309 74 57700 0 0 0.9132 150 1038  26382.54 213 [(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0139 14 78000 0 0.15 0.9180 320 NDND ND 214 [(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0147 18 78800 0 0.33 0.9331 320 NDND ND 215 [(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0090 14 82100 ND ND ND 520 ND NDND 216 [(iPr₂Ph₂)DABAn]Ni(hfacac) 0.0142 25 96900 0 0 0.9205 580 4201425 3.4  217 [(Me₂Ph₂)DABH₂]Ni(hfacac) 0.0100  9 138000  5.6 215 0.9450630 ND ND ND 218 [(iPr₂Ph₂)DABMe₂]Ni(hfacac 0.0204 30 149000  0 0 0.8951370 516 1687 3.27 219 [(iPr₂Ph₂)DABMe₂]Ni(hfacac 0.0134 35 199000  0 00.9002 450 360 1523 4.23

[0067] TABLE 3 (all Runs were at 60° C. Run Run Mass Time ProductivityDensity # Catalyst cat. (g) (mins.) (g PE/g Ni) MI HLMI (g/cc) Al:Ni MnMw HI 301 [(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0161 6  1580 ND ND ND 280 ND ND ND302 [(Me₂Ph₂)DABH₂]NiCl₂ 0.0229 1  3810 1.7 112 0.9618 150  17  84 4.91303 [(Me₂Ph₂)DABMe₂]NiCl₂ 0.0545 16  4710 0.21 22 0.9056  26  33  942.82 304 [(Me₂Ph₂)DABH₂]NiCl₂ 0.0274 8  5130 2.5 126 0.9546  73  16  734.46 305 [(Me₂Ph₂)DABH₂]NiCl₂ 0.0233 8  5470 2.6 127 0.9530  58 ND ND ND306 [(iPr₂Ph₂)DABAn]NiBr₂ 0.0483 22  8660 0 0.11 0.8963 130 143 550 3.86307 [(iPr₂Ph₂)DABAn]NiCl₂ 0.0283 11  8740 0 0 0.8957 190 220 808 3.68308 [(iPr₂Ph₂)DABMe₂]NiBr₂ 0.0188 15 10200 0 0 0.8753 280 632 1725  2.73309 [(Me₂Ph₂)DABMe₂]NiBr₂ 0.0283 11 10400 0.26 16 0.9095 150  38 1102.92 310 [(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0085 6 10600 ND ND ND 520 ND ND ND311 [(Me₂Ph₂)DABH₂]NiBr₂ 0.0312 9 12600 4.4 169 0.9527 130  15  86 5.93312 [(Me₂Ph₂)DABMe₂]NiCl₂ 0.0328 5 13100 0.03 5.5 0.9107 110  53 1643.10 313 [(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0313 7 17000 ND ND ND 150 ND ND ND314 [(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0202 7 17100 0 0 0.8817 220 390 1228  3.15315 [(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0158 5 18400 0.02 3.0 0.9215 300 ND NDND 316 [(iPr₂Ph₂)DABMe₂]NiCl₂ 0.0185 17 52100 0 0 0.8805 250 ND ND ND317 [(iPr₂Ph₂)DABAn₂]Ni(hfacac)₂ 0.0048 16 104000  0 0.08 0.9011 1700 309 1366  4.4  318 [(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0088 19 116000  0 00.8867 680 ND ND ND 319 [(Me₂Ph₂)DABH₂]Ni(hfacac)₂ 0.0034 4 137000  1.378 0.9569 1850  ND ND ND 320 [(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0029 14302000  0 0 0.8986 2600  788 2389  3.0 

[0068] TABLE 4 (all Runs were at 80° C. Run Run Mass Time ProductivityDensity # Catalyst cat. (g) (mins) (gPE/gNi) MI HLMI (g/cc) Al:Ni Mn MwHI 401 [(iPr₂Ph₂)DABAn]NiCl₂ 0.0326 9 1980 ND ND 0.9048 160 ND ND ND 402[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0161 3 3860 0.46 24 0.9246 280 ND ND ND 403[(iPr₂Ph₂)DABAn]NiBr₂ 0.0239 5 4580 0 1.5 0.8644 260 ND ND ND 404[(Me₂Ph₂)DABH₂]NiBr₂ 0.0318 6 5160 16 ND 0.9466 130  12  44 3.62 405[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0253 3 6650 1.5 67 0.9118 180 ND ND ND 406[(iPr₂Ph₂)DABMe₂]NiBr₂ 0.0363 5 6740 0 0 0.8680 150 255 652 2.56 407[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0131 4 7140 ND ND ND 360 ND ND ND 408[(Me₂Ph₂)DABMe₂]NiBr₂ 0.0263 9 9920 72 ND ND 160  14  31 2.22 409[(Me₂Ph₂)DABH₂]Ni(hfacac)₂ 0.0035 2 10800  ND ND 0.9997 1800  ND ND ND410 [(iPr₂Ph₂)DABAn₂]Ni(hfacac)₂ 0.0202 4 24600  0 0.12 0.8899 410 145644 4.4  411 [(iPr₂Ph₂)DABMe₂]Ni(hfacac)Cl 0.0088 4 25700  0 0.04 0.8867680 ND ND ND 412 [(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0059 4 83600  0 0 0.89121300  394 171 4.3 

[0069] The results in Tables 2,3, and 4 show that the high productivityseen with nickel diimine complexes containing one or two β-diketonate orβ-ketoester ligands is maintained when temperature (and thereforedissolved ethylene concentration as well) and the diimine ligand arechanged. Again, note that reactor temperatures were within commerciallyacceptable ranges, i.e., between 40 and 80° C.

Example 3

[0070] This example shows that the high productivity seen with diiminenickel complexes containing one or two β-ketoester ligands is maintainedat low Al:Ni ratios; i.e., low levels of MAO. Again, all of thefollowing polymerizations were carried out as described above, with areactor pressure of 550 psig ethylene in isobutane slurry. MAO was addedin a 10% wt/wt solution in toluene. Catalyst system used in Runs 523-527were physically mixed with an inert, filler material before addition tothe reactor in order to expedite weighing small amounts of catalystsystem. Then, the actual mass of catalyst system added to the reactorwas calculated, based on the weight ratio of filler and catalyst systemcombined. TABLE 5 Run Run Mass T Time Productivity Density # Catalystcat. (g) (° C.) (mins) (g PE/g Ni) MI HLMI (g/cc) Al:Ni 501[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0110 13 9 87200 0 0.19 0.9348 160 502[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0362 27 11 29000 0 0.45 0.930  120 503[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0147 27 17 78800 0 0.33 0.9331 320 504[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0139 27 10 78000 0 0.15 0.9180 320 505[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0204 27 30 149000  0 0 0.8951 370 506[(iPr₂Ph₂)DABMe₂]Ni(hfacac)Cl 0.0134 27 35 199000  0 0 0.9002 450 507[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0090 27 14 82100 ND ND ND 520 508[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0448 40 7 28500 0 0.34 0.9221 100 509[(Me₂Ph₂)DABH₂]Ni(hfacac)₂ 0.0050 40 5 52700 1.5 51 0.9608 250 510[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0185 40 10 51800 0 0.12 0.9360 250 511[(iPr₂Ph₂)DABMe₂]Ni(allOacac)₂ 0.0209 40 27 21300 0 0 0.9157 300 512[(iPr₂Ph₂)DABMe₂]Ni(PhCF₃acac)₂ 0.0165 40 41 33700 0 0 0.9137 460 513[(iPr₂Ph₂)DABMe₂]Ni(CF₃CF₂CF₂tBuacac)₂ 0.0608 60 7 4430 0 0 <0.8800  150514 [(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0313 60 7 17000 ND ND ND 150 515[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0158 60 5 18400 0.02 3.0 0.9215 300 516[(iPr₂Ph₂)DABMe₂]Ni(allOacac)₂ 0.0177 60 4  6450 0 0 0.9060 360 517[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0253 80 3  6650 1.5 67 0.9118 180 518[(iPr₂Ph₂)DABMe₂]Ni(CF₃furacac)₂ 0.0310 80 6  8600 0 0.08 0.8836 240 519[(Me₂Ph₂)DABH₂]Ni(acac)₂ 0.0161 80 3  3900 0.46 24 0.9246 280 520[(iPr₂Ph₂)DABMe₂]Ni(PhCF₃acac)₂ 0.0216 80 4 12000 0 0.04 0.9013 350 521[(Me₂Ph₂)DABMe₂]Ni(acac)₂ 0.0131 80 4  7140 ND ND ND 360 522[(iPr₂Ph₂)DABAn]Ni(hfacac)₂ 0.0202 80 4 24600 0 0.12 0.8899 410 523[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0038 40 16 116000  ND ND ND 1590  524[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0054 40 10 53000 ND ND ND 830 525[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0046 40 20 169000  ND ND ND 660 526[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0044 40 47 104000  ND ND ND 340 527[(iPr₂Ph₂)DABMe₂]Ni(hfacac)₂ 0.0052 40 28 99000 ND ND ND 140

[0071] The data in Table 5 show that high productivity can be achievedwith diimine nickel complexes containing one or two β-diketonate orβ-ketoester groups with low levels of MAO. Runs 523-527 clearlydemonstrate that very high productivities can be achieved even at verylow Al:Ni molar ratios, i.e., low amounts of MAO added to thepolymerization reaction.

Example 4

[0072] This Example shows that inventive catalyst systems can be used toproduce syndiotactic polymers. The term “syndiotactic polymer”, as usedherein, includes those polymers having segments of more than 10monomeric units in which the alkyl groups of each successive monomericunit is on the opposite side of the plane of the polymer. Syndiotacticpolymers produced according to the invention can have a wide range ofapplications based upon their physical properties. These syndiotacticpolymers can be molded by heat to form shaped objects and they can beused to form fibers or filaments. These syndiotactic polymers also canbe used for blending with polymers of different tacticity to vary theproperties of such polymers.

[0073] In this example where information is given about themicrostructure of polymers as determined by ¹³CNMR, spectra were takenusing standard accepted spectroscopy techniques. Polymer was dissolvedin 1,2,4-trichlorobenzene and the spectra was taken with respect to aninternal standard relative to hexamethylsiloxane which has a knownreference point relative to tetramethylsilane; the base standard in theNMR spectra was 0 ppm based on tetramethylsilane. From the observedintegrals of the relevant peaks, the details regarding themicrostructure are calculated. $\begin{matrix}{{{Randomness}\quad {Index}} = \frac{({mr})\quad 100}{2(m)(r)}} \\{{{Average}\quad {Isotactic}\quad {Block}\quad {Length}} = {1 + \frac{2({mm})}{({mr})}}} \\{{{Average}\quad {Syndiotactic}\quad {Block}\quad {Length}} = {1 + \frac{2({rr})}{({Mr})}}}\end{matrix}$

[0074] For more detail regarding the determination of these values,reference can be made to Chapter 3 of Chain Structure and Conformationof Macromolecules (Academic Press, 1982) by Frank A. Bovey.

[0075] Polymerization was carried out as described above. Reactortemperature was 80° C. 0.0140 g ofN,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine nickel(II)bis(acetylacetonate), designated as [(iPr₂Ph)₂DABMe₂]Ni(acac)₂ thenickel catalyst system and 5 mls of MAO (10 weight % in toluene) wereadded to the reactor, followed by propylene. Propylene was fed on demandand the polymerization reaction terminated when propylene flow into thereactor ceased. Hydrogen was not added to the reactor. After one hour ofreaction time, isobutane was removed to yield 4.2 g of polymer.Productivity was 2660 g polypropylene/g Ni. Polymer characterization by¹³CNMR is as follows.

[0076] %[mm]=6.00

[0077] %[m]=17.1

[0078] %[mr]=22.17

[0079] %[r]=7.48

[0080] %[rr]=71.83

[0081] The above data demonstrates that the inventive catalyst systemscan produce syndiotactic polymers, such as syndiotactic polypropylene,as shown by approximately 72% rr triads as determined by ¹³CNMRspectroscopy.

[0082] While this invention has been described in detail for the purposeof illustration, it is not to be construed as limited thereby but isintended to cover all changes and modifications within the spirit andscope thereof.

That which is claimed:
 1. A polymerization process comprising contactingin a reaction zone under slurry polymerization reactor conditions: a)ethylene monomer and b) heterogenous catalyst system comprisingmethylaluminoxane and one or more diimine, nickel complexes whereinnickel complex comprises additional ligands selected from the groupconsisting of α-deprotonated-β-diketones, α-deprotonated-β-ketoesters,halogens and mixtures thereof having a formula selected from the groupconsisting of Ni(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)₂ and Ni(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)Z; wherein a polymer is recovered.
 2. A processaccording to claim 1 further comprising contacting a comonomer selectedfrom the group consisting of alpha-olefins having from 3 to 10 carbonatoms per molecule with (a) and (b).
 3. A process according to claim 2wherein said comonomer is selected from the group consisting ofpropylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene,and mixtures thereof.
 4. A process according to claim 3 wherein saidcomonomer is selected from the group consisting of 1-hexene,4-methyl-1-pentene, and mixtures thereof.
 5. A process according toclaim 1 wherein said diimine nickel complex is represented by theformulas selected from the group consisting of

wherein R can be the same or different and is selected from the groupconsisting of branched or linear alkyl aromatic groups having from about1 to about 10 carbon atoms per alkyl group and can be in any position onthe aromatic ring; wherein R′ can be the same or different and isselected from the group consisting of hydrogen and linear, branched,cyclic, bridging, aromatic, and/or aliphatic hydrocarbons, having fromabout 1 to about 70 carbon atoms per radical group; wherein R″CYCXCYR″can be the same or different and is selected from the group consistingof α-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof, and wherein R″ and X can be the same or different andare selected from the group consisting of hydrogen and linear, branched,cyclic, bridging, aromatic, aliphatic hydrocarbons, and mixtures thereofhaving from about 1 to about 70 carbon atoms per radical group,optionally containing atoms other than carbon and hydrogen; wherein Yand be the same or different and is selected from the group consistingof oxygen, sulfur, or selenium; and wherein Z is a halogen selected fromthe group consisting of fluorine, chlorine, bromine, and iodine.
 6. Aprocess according to claim 5 wherein said R substituent is selected fromthe group consisting of linear or branched alkyl groups having fromabout 1 to about 8 carbon atoms per group.
 7. A process according toclaim 6 wherein said R substituent is selected from the group consistingof methyl groups, isopropyl groups, and mixtures thereof.
 8. A processaccording to claim 5 wherein said R′ substituent is selected from thegroup consisting of hydrogen and branched, linear, cyclic, aromatic andaliphatic hydrocarbon radicals and mixtures thereof having from about 1to about 20 carbon atoms per radical.
 9. A process according to claim 8wherein said R′ substituent is selected from the group consisting ofhydrogen, methyl groups, ethyl groups, propyl groups, phenyl groups,acenaphthyl groups, cyclobutadienyl groups and mixtures thereof.
 10. Aprocess according to claim 5 wherein one said R″ and X are selected fromthe group consisting of hydrogen and linear, branched, cyclic, bridging,aromatic, aliphatic hydrocarbon radicals, and mixtures thereof havingfrom about 1 to about 70 carbon atoms per radical group, optionallycontaining atoms other than carbon and hydrogen and wherein the othersaid R″ is selected from the group consisting of alkoxides of linear,branched, cyclic, bridging, aromatic, and aliphatic hydrocarbonradicals, and mixtures thereof having from about 1 to about 70 carbonatoms per radical group, optionally containing atoms other than carbonand hydrogen.
 11. A process according to claim 5 wherein said R″CYCXCYR″can be the same or different and is selected from the group consistingof β-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof, and wherein R″ and X can be the same or different andare selected from the group consisting of hydrogen and linear, branched,cyclic, bridging, aromatic, aliphatic hydrocarbons, and mixtures thereofhaving from about 1 to about 10 carbon atoms per radical group,optionally containing atoms other than carbon and hydrogen.
 12. Aprocess according to claim 11 wherein one said R″ and X is selected fromthe group consisting of hydrogen and linear, branched, cyclic, bridging,aromatic, aliphatic hydrocarbons, and mixtures thereof having from about1 to about 10 carbon atoms per radical group, optionally containingatoms other than carbon and hydrogen and wherein the other R″ isselected from the group consisting of the alkoxides of linear, branched,cyclic, bridging, aromatic, aliphatic hydrocarbons, and mixtures thereofhaving from about 1 to about 10 carbon atoms per radical group,optionally containing atoms other than carbon and hydrogen.
 13. Aprocess according to claim 5 wherein said R″CYCXCYR″ is selected fromthe group consisting of 2,4-pentanedione,1,1,1,5,5,5-hexafluoro-2,4-pentanedione, allylacetonacetate,benzoylacetonate, benzoyl-1,1,1-trifluoroacetone,1,1,1-trifluoro-2,4-pentanedione, 1-chloro-1,1-difluoroacetylacetonemethyl-4,4,4-trifluoroacetoacetate,1,1,1-trifluoro-5,5-dimethyl-2,4-pentanedione, ethylalpha-methyl-4,4,4-trifluoroacetoacetate,4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, and2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione; and Z isselected from the group consisting of chloride and bromide.
 14. Aprocessing according to claim 1 where in said aluminum to nickel molarratio is within a range of about 50:1 to about 1200:1.
 15. A processaccording to claim 1 wherein said slurry polymerization reactorconditions comprise a reaction temperature within a range of about 10°to about 90° C. and a pressure within a range of about 100 to about 1000psia.
 16. A process according to claim 1 wherein said slurrypolymerization reactor conditions comprise a diluent of isobutane.
 17. Aheterogeneous catalyst composition comprising: a) diimine nickelcomplexes having a formula selected from the group consisting of

 wherein R can be the same or different and is selected from the groupconsisting of branched or linear alkyl or aromatic groups having fromabout 1 to about 10 carbon atoms per alkyl group and can be in anyposition on the aromatic ring; wherein R′ can be the same or differentand is selected from the group consisting of hydrogen and linear,branched, cyclic, bridging, aromatic, and/or aliphatic hydrocarbons,having from about 1 to about 12 carbon atoms per radical group; whereinR41 CYCXCYR″ can be the same or different and is selected from the groupconsisting of α-deprotonated-β-diketones, α-deprotonated-β-ketoesters,halogens and mixtures thereof, and wherein R″ and X can be the same ordifferent and are selected from the group consisting of hydrogen andlinear, branched, cyclic, bridging, aromatic, aliphatic hydrocarbons,and mixtures thereof having from about 1 to about 10 carbon atoms perradical group, optionally containing atoms other than carbon andhydrogen; wherein Y and be the same or different and is selected fromthe group consisting of oxygen, sulfur, or selenium; and wherein Z is ahalogen selected from the group consisting of fluorine, chlorine,bromine, and iodine and b) methylaluminoxane.
 18. A compositionaccording to claim 17 wherein said R substituent is selected from thegroup consisting of linear or branched aliphatic groups having fromabout 1 to about 8 carbon atoms per group.
 19. A composition accordingto claim 18 wherein said R substituent is selected from the groupconsisting of methyl groups, isopropyl groups, and mixtures thereof. 20.A composition according to claim 17 wherein said R′ substituent isselected from the group consisting of hydrogen and branched, linear,cyclic, aromatic or aliphatic hydrocarbon radicals having from about 1to about 12 carbon atoms per radical.
 21. A composition according toclaim 20 wherein said R′ substituent is selected from the groupconsisting of hydrogen, methyl groups, ethyl groups, propyl groups,phenyl groups, acenaphthyl groups, cyclobutadienyl groups and mixturesthereof.
 22. A composition according to claim 17 wherein one said R″ andX are selected from the group consisting of hydrogen and linear,branched, cyclic, bridging, aromatic, aliphatic hydrocarbon radicals,and mixtures thereof having from about 1 to about 70 carbon atoms perradical group, optionally containing atoms other than carbon andhydrogen and wherein the other said R″ is selected from the groupconsisting of alkoxides of linear, branched, cyclic, bridging, aromatic,and aliphatic hydrocarbon radicals, and mixtures thereof having fromabout 1 to about 70 carbon atoms per radical group, optionallycontaining atoms other than carbon and hydrogen; and Z is selected fromthe group consisting of fluorine, chlorine, bromine, and iodine.
 23. Acomposition according to claim 22 wherein said R″CYCXCYR″ is selectedfrom the group consisting of 2,4-pentanedione,1,1,1,5,5,5-hexafluoro-2,4-pentanedione, allylacetonacetate,benzoylacetonate, benzoyl-1,1,1-trifiuoroacetone,1,1,1-trifluoro-2,4-pentanedione, 1-chloro-1,1-difluoroacetylacetonemethyl-4,4,4-trifluoroacetoacetate,1,1,1-trifluoro-5,5-dimethyl-2,4-pentanedione, ethylalpha-methyl-4,4,4-trifluoroacetoacetate,4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione,2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione, and mixturesthereof; and Z is selected from the group consisting of chloride andbromide.
 24. A composition according to claim 17 wherein said diiminenickel complexes and said methylaluminoxane are present in an amount tohave an aluminum to nickel molar ratio of less than about 850:1.
 25. Acomposition according to claim 17 wherein said aluminum to nickel molarratio is within a range of about 50:1 to about 600:1.
 26. A polymercomposition of ethylene comprising from 20 to 3000 short chain branchesper 10,000 backbone carbon atoms of said polymer; and wherein saidpolymer has a heterogeneity index in the range of about 3 to about 8.27. A polymerization process comprising contacting in a reaction zoneunder slurry polymerization reactor conditions: a) propylene monomer andb) a heterogenous catalyst system comprising methylaluminoxane and oneor more diimine nickel complexes wherein nickel complex comprisesadditional ligands selected from the group consisting ofα-deprotonated-β-diketones, α-deprotonated-β-ketoesters, halogens andmixtures thereof having a formula selected from the group consisting ofNi(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)₂ and Ni(NCR′C₆R₂H₃)₂(Y₂C₃R″₂X)Z; wherein apolymer is recovered.
 28. A process according to claim 27 furthercomprising contacting a comonomer selected from the group consisting ofalpha-olefins having from 2 to 10 carbon atoms per molecule with (a) and(b).
 29. A processing according to claim 27 wherein said recoveredpolymer is syndiotactic polypropylene.